DE60312615T2 - Thiophene derivatives and corresponding optical elements - Google Patents

Abstract

A compound represented by the following general formula (I) or (I A), and an optical element, a non-linear optical material and an electro-optical material containing the compound or a polymer thereof. <CHEM> <CHEM>

Description

The The present invention relates to a novel compound which is useful as an electro-optic material or a non-linear optical Material used in the field of optoelectronics and photonics becomes. The invention also relates to different types of optical Elements such as phase difference plates and electro-optic Equipment, which exploit the non-linear optical effect.

Description of the related State of the art

What Non-linear optical materials, the search for new materials and device manufacturing mainly in the field of inorganic non-linear optical materials carried out. In In recent years, however, organic, nonlinear optical Attention: materials because of their following properties: (1) big optical nonlinearity, (2) fast response, (3) high threshold for optical damage, (4) ability to the manifold Molecular design and (5) excellent adaptability to the production. The development for the secondary, non-linear optical effect requires that induced by electric fields Polarization should not have centrosymmetry. It is appropriate necessary, molecules, which show a nonlinear optical effect or groups with nonlinear optical response in such a structure in the To arrange material that has no centrosymmetry.

Around molecules which have a non-linear optical effect or groups with non-linear ones to arrange optical response in the structure that does not have centrosymmetry It has become common exploited, the molecules, which show the nonlinear optical effect or the groups with to incorporate nonlinear optical response into an organic polymer, and for example by electric fields to orient the dipoles. This is a method of orienting the dipoles of molecules or Response groups representing the secondary non-linear optical Show effect by applying a high voltage at a temperature above the Glass transition point of a base polymer and then freezing the orientation of the Dipoles by cooling. SPIE Journal, Vol. 1213, page 7 (1990) gives some examples of electro-optic (EO) -Modulationsgeräte, which were produced by this method. Such a material however, thermally causes orientation relaxation over time, worsens in the electro-optical properties and it lacks in the result of stability. Thus, it can not be used practically or on a wide range of use be applied. His solution was desired Cryst., Liq., Cryst., Journal, Vol. 189, page 3 (1990)). Furthermore, the long-term stability was not sufficiently ensured and further improvement was desired in this regard.

Further discloses Appl. Phys. Lett. Journal, Vol. 34, page 423 (1979) Example using 5CB (4-cyano-4'-pentylbiphenyl) as a rod-shaped liquid crystal compound for a non-linear optical material. The rod-shaped liquid crystal compound, such as for example 5CB, was in the non-linear optical properties at the molecular level bad if considered as a non-linear optical material was used, and there was a need for one new compound with better non-linear optical properties.

The The present invention is intended to solve the aforementioned problems of the prior art solve the technology and achieve the following goals. That is, the invention intends (1) a new compound that is useful is considered a non-linear optical material that is organic Material with no or controlled orientation relaxation includes, (2) a new compound useful as a nonlinear one optical material, the second harmonic waves in the orientation forms in electric fields, and (3) an optical element, a non-linear one optical material and an electro-optical material using a crosslinked or non-crosslinked body of the compound put.

The Inventors have found that these objects are described below Invention can be achieved.

A first aspect of the invention provides a compound represented by the following general formula (I):

In the general formula (I), -Ar ² -AS ² -P ² substituted at the 4-position or 5-position of a thio phenrings. Ar ¹ and Ar ² each independently represent a single bond, an aromatic ring having 5 to 14 carbon atoms, or a biphenyl group, provided that at least one of Ar ¹ and Ar ² denotes one of a naphthalene ring and a biphenyl group which may have a substituent , D denotes an oxygen atom (-O-), a sulfur atom (-S-), a substituted amino group (-NR-) in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or one represented by P ¹ -S ¹ - Substituents, or an amino group having a cyclic structure. A denotes an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfonyloxy group (-SO ₃ -).

Each of S ¹ and S ² independently denotes a divalent linking group. Each of P ¹ and P ² independently denotes a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom, and at least one of P ¹ and P ² denotes a polymerizable group containing an acryloyloxy group or a methacryloyloxy group includes. The thiophene ring may have a substituent.

One second aspect of the invention provides an optical element which the compound of the first aspect or a polymer of the compound contains.

One third aspect of the invention provides a non-linear optical Material or an electro-optical material available, the the compound of the first aspect or by polymerization the compound formed polymer contains.

A fourth aspect of the invention provides a compound represented by the following general formula (IA):

In the general formula (IA), -Ar ² -P ⁴ substitutes at the 4-position or 5-position of a thiophene ring. Ar ¹ and Ar ² each independently denotes a single bond, an aromatic ring having 5 to 14 carbon atoms or a biphenyl group, provided that at least one of Ar ¹ and Ar ^{2 is} one of a naphthalene ring and a biphenyl group which may have a substituent; represents. P ³ denotes a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein one or more -CH ₂ - in the alkyl group may be replaced by -O-, -CO-, -NR ¹ -, in the R ^{1 is} a linear is a branched or cyclic alkyl group having 1 to 20 carbon atoms, -CH = CH- or -C≡C-, provided that heteroatoms are not adjacent to each other, and the alkyl group may have a substituent consisting of atoms which are selected from C, H, O, N, S and a halogen atom. P ⁴ represents -P ^{4 '} -P ⁶ , wherein:
P ^{6 represents} a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein one or more of the -CH ₂ - in the alkyl group may be replaced by -O-, -CO-, -CH = CH- or -C≡C with the proviso that heteroatoms are not adjacent to each other and the alkyl group may have a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom; and P ^{4 'represents} a divalent electron-attracting group selected from the group consisting of an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfoxy group (-SO ₃ -). D ¹ denotes one selected from the group consisting of an oxygen atom (-O-), a sulfur atom (-S-) and -NP ⁵ -. Here, P ^{5 represents} a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein one or more of -CH ₂ - in the alkyl group by -O-, -CO-, -CH = CH- or -C≡ C - can be replaced, provided that heteroatoms are not adjacent to each other and the alkyl group may have a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom. P ⁵ may be independent of P ³ or bound to P ^{3 to form} a ring. The thiophene ring may have a substituent.

One fifth Aspect of the invention provides an optical element which the compound of the fourth aspect or a polymer thereof.

One Sixth aspect of the invention provides a non-linear optical Material or an electro-optic material prepared that the connection of the fourth aspect or by polymerization of the compound formed polymer.

1 FIG. 16 is a view showing a first example of a layer structure of a non-linear optical Ma. FIG terials in the present invention shows.

2 Fig. 14 is a view showing a second example of a layer structure of a non-linear optical material in the present invention.

3 Fig. 12 is a view showing the change of the intensity of the second harmonic waves (SH waves) before and after the corona poling of Compound 2 (Maker Fringe view).

4 FIG. 12 is a view showing the intensity of the second harmonic waves (SH waves) between connection 23 and 5CB (maker-fringe view).

The The present invention will be described below in detail.

The novel compound of the invention is represented by the following general formula (I):

In the general formula (I), Ar ¹ and Ar ² each independently denote a single bond, an aromatic ring having 5 to 14 carbon atoms or a biphenyl group, provided that at least one of Ar ¹ and Ar ^{2 is} one of a naphthalene ring and a biphenyl group which may have a substituent represents. D denotes an oxygen atom (-O-), a sulfur atom (-S-), a substituted amino group (-NR-) in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or one represented by P ¹ -S ¹ - Substituents, or an amino group having a cyclic structure. A denotes an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfonyloxy group (-SO ₃ -). Each of S ¹ and S ² independently represents a divalent linking group. P ¹ and P ² each independently represent a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom, and at least one of P ¹ and P ² represents a polymerizable group. The thiophene ring may have a substituent. Ar ¹ or Ar ² in the general formula (I) is preferably an aromatic ring having 5 to 14 carbon atoms (a ring having aromaticity including a hetero ring having 5 or more carbon atoms) or a biphenyl group, and more preferably a benzene ring, a naphthalene ring or a biphenyl group. It is particularly preferable that one of Ar ¹ and Ar ^{2 is} a naphthalene ring. In particular, it is particularly preferred that Ar ^{1 is} a benzene ring and Ar ^{2 is} a naphthalene ring or Ar ^{1 is} a naphthalene ring and Ar ^{2 is} a benzene ring. When Ar ¹ or Ar ² denotes an aromatic ring having a substituent, examples of preferred substituents include lower alkyl groups having 1 to 6 carbon atoms, and more preferably include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group and Hexyl group.

D in the general formula (I) is an oxygen atom (-O-), a sulfur atom (-S-), -NH- as an electron donating group, a substituted amino group (-NR-) in which R is preferably a substituent of one lower alkyl having 1 to 6 carbon atoms or a -wiedergegebener by P ¹ -S ¹ substituent, and R particularly preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl is a hexyl group or the like, or an amino group having one of the following cyclic structures:

D is particularly preferably an oxygen atom.

A denotes an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfonyloxy group (-SO ₃ -). A is preferably an ester group (-COO-) or a sulphonyloxy group (-SO ₃ -).

The linking groups represented by S ¹ and S ² in the general formula (I) preferably have 2 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Further, S ¹ and S ^{2 may} also have a cyclic structure, and a cyclohexyl ring is preferable if they have the cyclic structure. Examples of linking groups include an alkylene group. The linking group can have one or more substituents. In this case, examples of the substituents include a substituent having 1 to 4 carbon atoms and a halogen atom. Particularly preferred are a methyl group, an ethyl group, a propyl group and an isopropyl group. Further, when the carbon atom having the substituent is an asymmetric carbon, its steric arrangement may be R, S or a mixture thereof in any proportion.

Each of P ¹ and P ² in the general formula (I) denotes a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom. At least one of P ¹ and P ² represents a polymerizable group including an acryloyloxy group or a methacryloyloxy group. Only one of P ¹ and P ² may be a polymerizable group, but it is preferred that P ¹ and P ² in the general formula (I) are both polymerizable groups. P ¹ and P ² include an acryloyloxy group and a methacryloyloxy group.

Further, the novel compound of the present invention can be represented by the following general formula (IA):

In the general formula (IA), Ar ¹ and Ar ^{2 have the} same meaning as described in the general formula (I). The thiophene ring may have a substituent.

D ¹ in the general formula (IA) denotes -O-, -S-, -NP ⁵ - in which P ^{5 represents} a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein one or more -CH ₂ - in the alkyl group may be replaced by -O-, -CO-, -CH = CH- or -C≡C-, with the proviso that heteroatoms are not adjacent to each other, and may have a substituent consisting of atoms , selected from C, H, O, N, S and a halogen atom, and P ⁵ may be independent of P ³ or may be bonded to P ³ to form a ring. Preferred examples of D1 include -O-, -NP ³ -, -NR-, wherein R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group or a hexyl group, or an amino group having one of the following cyclic structures:

D ¹ is particularly preferably -O-, -NP ¹ - or -NR-, wherein R represents a methyl group, an ethyl group, a propyl group or an isopropyl group.

P ³ in the general formula (IA) denotes a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. One or more -CH ₂ - in the alkyl group may be represented by -O-, -CO-, -NR ¹ -, wherein R ¹ denotes a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, -CH = CH- or -C ≡C-, with the proviso that heteroatoms are not adjacent to each other. P ³ may have a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom. Examples of P ³ include a linear, branched or cyclic alkyl group wherein one or a plurality of hydrogen atom (s) may be replaced at any position by a halogen atom, a polyethyleneoxy group or the following polymerizable substituents (q is an integer):

q is preferably 2 to 14, more preferably 2 to 10, and still more preferably 4 to 10. P ³ is particularly preferably a linear or branched alkyl group having 1 to 14 carbon atoms, and more preferably a linear alkyl group having 1 to 12 carbon atoms.

Examples of P ⁴ include the following substituent groups:

-P ⁴ in the general formula (IA) denotes -P ^{4 '} -P ⁶ , P ⁶ denotes a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, one or more -CH ₂ - in the alkyl group being substituted by -O- , -CO-, -CH = CH- or -C≡C-, with the proviso that heteroatoms are not adjacent to each other, and the alkyl group may have a substituent consisting of atoms selected from C, H , O, N, S and a halogen atom, and -P ^{4 '} - denotes a divalent electron-attracting group consisting of atoms selected from the group consisting of an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfoxy group (-SO ₃ -).

Examples of P ⁶ include a linear, branched or cyclic alkyl group (one or more hydrogen atom (s) at an arbitrary position may be replaced by a halogen atom), a polyethyleneoxy group and the following polymerizable substituent groups (q is an integer):

q is preferably 2 to 14, more preferably 2 to 10 and even more preferably 4 to 10.

Examples of P ^{4 '} include an ester group (-COO-), a sulfonyl group (-SO ₂ -), a sulfoxy group (-SO ₃ -) or the following substituents:

-Ar ² -AS ² -P ² in the general formula (I) and -Ar ² -P ⁴ in the general formula (IA) substitute at the 4-position or 5-position of the thiophene ring and according to the invention they preferably substitute at the 5 And in particular, the compounds represented by the general formulas (I) and (IA) are preferably the compounds represented by the following general formulas (II) and (II-A).

In the general formula (II), Ar ¹ , Ar ² , D, A, S ¹ , S ² , P ¹ and P ^{2 have the} same meanings as described above.

In the general formula (II-A), Ar ¹ , Ar ² , D ¹ , A ¹ , P ³ and P ^{6 have the} same meanings as in the general formula (IA).

• (1) Ar¹ ist ein Benzolring und Ar² ist ein Naphthalinring oder Ar¹ ist ein Naphthalinring und Ar² ist ein Benzolring.
• (2) S¹ und S² bezeichnen jeweils unabhängig eine Alkylengruppe mit 2 bis 12 Kohlenstoffatomen.
• (3) P¹ und P² bezeichnen jeweils unabhängig eine Acryloyloxygruppe oder Methacryloyloxygruppe.
• (4) D bezeichnet ein Sauerstoffatom (-O-), Schwefelatom (-S-), eine substituierte Aminogruppe (-NR-), in der R ein Wasserstoffatom, eine Niederalkylgruppe mit 1 bis 6 Kohlenstoffatomen oder einen Substituenten, der durch P¹-S¹- wiedergegeben ist, bezeichnet, welche eine Aminogruppe mit einer cyclischen Struktur sein kann. A bezeichnet eine elektronenanziehende Gruppe, die ausgewählt ist aus einer Estergruppe (-COO-), einer Sulfonylgruppe (-SO₂-) und einer Sulfonyloxygruppe (-SO₃-).

In the general formula (I), a compound satisfying a combination of the following constitutions (1) to (4) is preferable:

• (1) Ar ¹ is a benzene ring and Ar ² is a naphthalene ring or Ar ¹ is a naphthalene ring and Ar ² is a benzene ring.
• (2) Each of S ¹ and S ² independently denotes an alkylene group having 2 to 12 carbon atoms.
• (3) Each of P ¹ and P ² independently denotes an acryloyloxy group or methacryloyloxy group.
• (4) D denotes an oxygen atom (-O-), sulfur atom (-S-), a substituted amino group (-NR-) in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms or a substituent represented by P ¹ -S ¹ -, which may be an amino group having a cyclic structure. A denotes an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfonyloxy group (-SO ₃ -).

• (1) Ar¹ ist eine 1,4-Phenylengruppe und Ar² ist eine 2,6-Naphthalingruppe oder Ar¹ ist eine 2,6-Naphthalingruppe und Ar² ist eine 1,4-Phenylengruppe.
• (2) P³ und P⁶ bezeichnen jeweils unabhängig eine Alkylgruppe mit 1 bis 16 Kohlenstoffatomen.
• (3) D¹ bezeichnet ein Sauerstoffatom (-O-), ein Schwefelatom (-S-), eine substituierte Aminogruppe (-NR-), in der R ein Wasserstoffatom, eine Niederalkylgruppe mit 1 bis 6 Kohlenstoffatomen oder einen Substituenten, der durch P³ wiedergegeben ist, bedeutet, oder eine Aminogruppe mit einer cyclischen Struktur. A¹ stellt eine elektronenanziehende Gruppe dar, die ausgewählt ist aus -COO-, -SO₂- oder -SO₃-.

In the general formula (II-A), a compound satisfying a combination of the following constitutions (1) to (3) is most preferable:

• (1) Ar ¹ is a 1,4-phenylene group and Ar ² is a 2,6-naphthalene group or Ar ¹ is a 2,6-naphthalene group and Ar ² is a 1,4-phenylene group.
• (2) Each of P ³ and P ⁶ independently denotes an alkyl group having 1 to 16 carbon atoms.
• (3) D ¹ denotes an oxygen atom (-O-), a sulfur atom (-S-), a substituted amino group (-NR-) in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms or a substituent substituted by P ^{3 represents} , or an amino group having a cyclic structure. A ¹ represents an electron attracting group selected from -COO-, -SO ₂ - or -SO ₃ -.

Examples the compound represented by the general formula (I) include the following compounds.

Examples the compound represented by the general formula (I-A) shut down the following compounds.

The preferred examples of the compounds of the present invention can be synthesized by the following methods of Schemes 1 and 2. However, the present invention should not be limited by these schemes. Scheme 1

In Scheme 1, Ar ¹ , Ar ² , D, S ¹ , S ² , P ¹ and P ^{2 have the} same meanings as described above and L denotes a leaving group and Y denotes a protecting group.

In the process of Scheme 1, when the compound represented by Compounds A and B (Compound B is preferably the equivalent amount of 1 to 2, and more preferably the equivalent amount of 1 to 1, 3 to the Compound A in the equivalent amount ratio) are used as starting materials, and in Presence of a Pd catalyst (the Pd catalyst is preferably 0.1 to 5 mol%, and more preferably 1 to 2 mol% based on the compound A) and the base I (the base I is preferably the equivalent amount of 1 to 4, and more preferably the equivalent amount of 1 to 2 to the compound B) in an organic solvent under an overheating condition at about 50 are stirred until 150 ° C for several hours, a compound which is represented by the compound C can be obtained. Examples of the protective group Y in the compound A include the tert-butoxycarbonyl (Boc) group, benzoylcarbonyl (Cbz) group, acetyl (Ac) group or the like, for example, when D is an amino group. When D is a substituent other than the one described above, the protection and deprotection can be carried out in accordance with the method as described in Protective Groups in Organic Chemistry, Plenum Press (London and New York, 1973); Green, TW, Protective Groups in Organic Synthesis, Wiley New York, 1981; and Peptides, Volume I, Schrooder and Lubke, Academic Press (London and New York, 1965).

Examples of the Pd catalyst used in the reaction are preferably Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ -PPh ₃ and Pd ₂ (dba) ₃ CHCl ₃ -PPh ₃ . For base I, inorganic and organic bases may be used and preferred examples of the base may include potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium acetate, sodium acetate and sodium phosphate. Examples of the organic solvent to be used include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), tetrahydrofuran (THF), chloroform, dichloromethane and dimethylsulfoxide (DMSO).

Then, when the compound C is in the presence of the base II (wherein the base II is preferably the equivalent amount of 1 to 2, and more preferably the equivalent amount of 1 to 1.2 to the compound C) at a low temperature of 0 ° C or below Stirred for several hours and then added dropwise B (OEt) ₃ and stirred at room temperature for several hours, a boronic acid compound represented by the compound D was obtained. Preferred examples of the base II include tert-butyllithium, n-butyllithium, lithium diisopropylamide (LDA), sodium hydride, lithium hydride and potassium carbonate, and particularly preferably include tert-butyllithium, n-butyllithium and lithium diisopropylamide (LDA).

Then, when the compound D and the compound represented by Br-Ar ² -CO ₂ Me are stirred in the presence of the Pd catalyst and the base I, the compound E can be obtained.

Then when the methyl ester of compound E is hydrolyzed by the method which is described in "Protective Groups in Organic Chemistry ", obtained the compound F.

Then, after thionyl chloride was added to the compound F, when the compound represented by HO-S ² -P ^{2 was} added dropwise and stirred for several hours, the compound G was obtained.

Then can, when the protective group Y of the compound G with the in "Protective Groups in Organic Chemistry " Deprotects the process the compound H will be obtained.

Finally, when the compound H is reacted with the compound represented by P ¹ -S ¹ -L in the presence of the base III, the target compound I is obtained. The preferred base III may include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and lithium hydroxide. Preferred examples of the leaving group L include halogen atom, alkylsulfonyloxy group or arylsulfonyloxy group. Scheme 2 (S ¹ and S ² are identical, and P ¹ and P ² are identical)

In Scheme 2, Ar ¹ , Ar ² and D have the same meanings as described above, L denotes a leaving group, Y denotes a protecting group, S denotes a spacer and P denotes a polymerizable group.

In the method of Scheme 2, when the compounds represented by compounds J and K represented compound (compound K is preferably in the equivalent amount 1 to 2, and more preferably the equivalent amount 1 to 1.3 to the compound J in an equivalent ratio) are used as the starting materials and in the presence of a Pd catalyst (The Pd catalyst is preferably 0.1 to 5 mol%, and more preferably 1 to 2 mol%, based on the compound J) and the base I (base I is preferably the equivalent amount 1 to 4 and more preferably the equivalent amount 1 to 2 to the compound B) in an organic solvent under an overheating condition at about 50 to 150 ° C for many Be stirred for hours, a compound represented by the compound L can be obtained. Examples of the protective group Y in the compound J include tert-butoxycarbonyl (Boc) group, Benzoylcarbonyl (Cbz) group, acetyl (Ac) group or the like, for example, when D is an amino group, a. If D is another Substituent is as described above, the shooter and deprotection in accordance carried out with the procedure as described in "Protective Groups in Organic Chemistry Journal".

Examples of the Pd catalyst used in the reaction are preferably Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ -PPh ₃ and Pd ₂ (dba) ₃ CHCl ₃ -PPh ₃ . For base I, inorganic and organic bases may be used and preferred examples of the base may include potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium acetate, sodium acetate and sodium phosphate. Examples of the organic solvent to be used include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), tetrahydrofuran (THF), chloroform, dichloromethane and dimethylsulfoxide (DMSO).

Then, when the compound L is in the presence of the base II (wherein the base II is preferably the equivalent amount of 1 to 2, more preferably the equivalent amount of 1 to 1.2 to the compound L) at a low temperature of 0 ° C or is stirred thereunder for several hours and then B (OEt) _{3 is} added dropwise and stirred at room temperature for several hours, a boronic acid compound represented by the compound M is obtained. Preferred examples of the base II include tert-butyllithium, n-butyllithium, lithium diisopropylamide (LDA), sodium hydride, lithium hydride and potassium carbonate, and particularly preferably include tert-butyllithium, n-butyllithium and lithium diisopropylamide (LDA).

Then, when the compound M and the compound represented by Br-Ar ² -CO ₂ Me are stirred in the presence of the Pd catalyst and the base I, the compound N can be obtained.

Then can, when the protective group Y of the compound N with the in "Protective Groups in Organic Chemistry " Deprotects the process will, the compound O will be obtained.

Finally, when compound O is the compound represented by P-S-L in the presence of the base III, the target compound P is obtained. The preferred base III may be sodium hydroxide, potassium hydroxide, potassium carbonate, Include sodium carbonate and lithium hydroxide. Preferred examples of Close leaving group L Halogen atom, alkylsulfonyloxy group or arylsulfonyloxy group.

The optical element as the application use of the compound of the present invention represented by the general formula (I) may include functional films (for example, optical films, ferroelectric films, anti-ferroelectric films, and piezoelectric films) and functional devices (e.g., non-linear optical devices, electro-optical devices, pyroelectric devices Devices, piezoelectric devices and optical modulation devices) used in the field of optics and the field of electronics. Specifically, in the application use of the non-linear optical devices (electro-optical devices), a waveguide-type device such as described in "Optical Wave Optics" edited by Corona Co., (1998), page 200, is manufactured. which is then used as an optical modulator for modulating the phase or intensity of optical waves or optical switches. Moreover, JP-A No. 9-22035 discloses an example of use in optical signal generators, and JP-A No. 2001-264715 discloses an example of the production of electric wave optical signal converters. Schmna 3

In Scheme 3, Ar ¹ , Ar ² , D, A and P ^{3 have the} same meanings as those for Scheme 2, L represents a leaving group and Y represents a protecting group. Compound D is synthesized in accordance with the Scheme 1 procedure , Then, when the compound D and the compound represented by Br-Ar ² -A are stirred in the presence of the Pd catalyst and the base I, the compound Q is obtained (the compound represented by Br-Ar ² - A is preferably the equivalent amount of 1 to 2, and more preferably the equivalent amount of 1 to 1.3 to the compound D in the equivalent amount ratio). Then, when the protective group Y of the compound Q is deprotected by the method described in "Protective Groups in Organic Chemistry", the compound R is obtained.

Finally, when the compound R is reacted with the compound represented by P ³ -L in the presence of the base III, the target compound S is obtained (the compound represented by P ³ -L is preferably the equivalent amount of 1 to 2, more preferably the equivalent amount of 1 to 1.3 to the compound R in the equivalent amount ratio). Preferred examples of the base III include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and lithium hydroxide. Preferred examples of the leaving group L may include halogen atom, alkylsulfonyloxy group or arylsulfonyloxy group. As the reaction solvent, the organic solvent used in Schemes 1 and 2 can be used.

(Optical element)

The Examples of an optical according to the invention Close element Functional films (for example, optical films, ferroelectric Films, anti-ferroelectric films, piezoelectric films) and Functional devices (for example non-linear optical devices, electro-optical devices, pyroelectric devices, piezoelectric devices and optical modulation devices), in the field of optics or in the field of electronics be used.

(Non-linear optical material and electro-optical material)

The non-linear optical material and the electro-optical material of the invention contain the compound of the present invention as at least one constituent component or otherwise contain a polymer polymerized from the compound of the present invention as at least one constituent component. When the compound of the present invention has a crosslinking group, the polymer polymerized from the compound of the present invention can be used as a non-linear optical material and an electro-optical material. The linear optical material and the electro-optical material of the invention include two embodiments. One is an embodiment in which the non-linear optical material and the electro-optical material alone are made of the compound of the present invention. The other is an embodiment in which the non-linear optical material and the electro-optical material are made of the compound of the present invention and a medium. The production methods thereof are shown below.

- Manufacturing process under Use of the compound of the invention alone -

The non-linear optical material and the electro-optical material The invention can be made by (1) applying as a layer or introducing a monomer composition containing the compound of the invention contains on a carrier or similar; (2) orienting them; and (3) crosslinking the same, while an orientation treatment is applied. In this case has the compound of the invention preferably a crosslinking substituent.

- Manufacturing process under Use of the compound of the invention and a medium -

The Material can be prepared by (1) dissolving a composition, the compound of the invention and a polymeric medium carrying same, or a composition, which contains a polymer of the compound according to the invention, in one Solvent; (2) Applying as a layer or placing it on a support followed from drying; and (3) applying an orientation treatment. In the shape of the optical according to the invention Elements, it is preferred, a layer containing the compound of the invention as at least part of the building component contains on to arrange a single substrate or between a pair of substrates.

in the Step of dissolution a composition containing the compound of the invention and the same Contains supporting polymer medium, or at the step of dissolution a composition comprising the polymer of the compound of the invention contains in a solvent, the polymeric medium is not particularly limited. Examples of these include acrylic polymer, such as PMMA, imide-type polymer such as fluoropolyimide, and polycarbonate one. Further, the solvent to be used is not special limited. Examples close to it solvent ester type such as ethyl acetate, ketone type solvent, such as methyl ethyl ketone, solvent ether-type, such as tetrahydrofuran and halogen-type solvents, such as chloroform and dichloromethane, as well as mixed solvents from that.

As a method of arranging a layer containing a compound having a non-linear optical response group (a part represented by D-Ar ¹ -thiophene ring-Ar ² -A in the general formula (I) or D ¹ -Ar ¹ -thiophene ring -Ar ² -P ^{4 is represented} in the general formula (IA)) as at least part of the constituent component, on a substrate, a well-known method is employed.

preferred Close examples of the substrate transparent substrates, such as glass, plastic film or reflection plate a, and a transparent electrode layer or an insulating film can optionally also be arranged on the substrate. A transparent one Electrode may or may not be provided, but ITO is, which is evaporated on the substrate, preferably, with no particular restriction thereon. The insulating film may or may not be provided and a polyimide type insulation film or polyvinyl alcohol insulation film is preferred when the insulating film is provided. Furthermore, in Case of using a pair of substrates spacers, sealants and the like may be used as appropriate.

One known method can for the coating applied and examples of the coating process shut down Curtain coating, extrusion coating, roll coating, Spin coating, dip coating, knife coating, spray coating, Slip coating and printing coating.

at The orientation treatment, the molecules are oriented by external electrical Fields or external magnetic Fields are created. As the orientation method is a method the use of external electrical Fields preferred and the use of Kontaktpolungsverfahrens (Plain electrode poling method, electrode sandwich poling method) or corona poling method is preferred.

If the compound of the invention has crosslinkable substituents, the polymer that forms the compound as one of the constituent components, with the following methods which are not to be understood as limiting the scope of the invention should be. For the formation of the polymer, various known Networking process for introduced crosslinkable substituents are suitable, can be applied. If for example, the crosslinkable substituent is an acryloyloxy group or methacryloyloxy group, is the radical polymerization of Use of a radical initiator, such as AIBN in an organic solvent particularly preferred.

It It is preferable that the compound of the present invention has a liquid crystal property has. When the compound of the invention the liquid crystal property shows, the application of the external electrical Fields or outer magnetic Fields preferably performed within a temperature range, the the liquid crystal phase shows. Further, there is also a method of heating to an isometric phase using external electric fields or external magnetic Fields and then cooling them on a liquid crystal phase prefers. What the intensity the external electric to be used Fields or outer magnetic Fields, becomes a suitable intensity for the orientation control used by liquid crystal molecules.

To the layer containing the crosslinkable compound as at least one Contains part of the structural components, may be a suitable polymerization initiator, polymerization inhibitor, Photosensitizer, crosslinker, liquid crystal orientation aid, etc. added become.

To be described below 1 and 2 show typical examples of a layer structure for the nonlinear optical material of the present invention. In the drawing are a non-linear optical response layer 1 , an isolation film 2 and a transparent electrode substrate 3 shown.

embodiments The present invention will be described as follows.

A first embodiment of the invention provides a compound represented by the following general formula (I):

In the general formula (I), -Ar ² -AS ² -P ² substituted at the 4-position or 5-position of the thiophene ring. Ar ¹ and Ar ² each independently represent a single bond, an aromatic ring having 5 to 14 carbon atoms, or a biphenyl group, provided that at least one of Ar ¹ and Ar ^{2 represents} one of a naphthalene ring and a biphenyl group which may have a substituent , D represents an oxygen atom (-O-), a sulfur atom (-S-), a substituted amino group (-NR-) in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms or a substituent represented by P ¹ - S ¹ -, denoted, or an amino group having a cyclic structure. A denotes an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfonyloxy group (-SO ₃ -). Each of S ¹ and S ² independently denotes a divalent linking group. Each of P ¹ and P ² independently denotes a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom. At least one of P ¹ and P ² denotes a polymerizable group. The thiophene ring may have a substituent.

A second embodiment of the invention provides the compound of the first embodiment in which Ar ^{1 represents} a benzene ring and Ar ^{2 represents} a naphthalene ring; or Ar ^{1 represents} a naphthalene ring and Ar ^{2 represents} a benzene ring.

A third embodiment of the invention provides the compound of the first or second embodiment in which S ¹ and S ² each independently represent an alkylene group having 2 to 12 carbon atoms.

A fourth embodiment of the present invention provides the compound of any of the first to third embodiments in which P ¹ and P ² each independently represent an acryloyloxy group or a methacryloyloxy group.

A fifth embodiment of the invention provides an optical element comprising the Compound one of the first to fifth embodiments or contains a polymer of the compound.

A sixth embodiment of the invention provides a non-linear optical material that the compound of any one of the first to fifth embodiments or a polymer formed by polymerizing the compound as at least contains a building component.

A Seventh embodiment of the invention provides an electro-optic material that facilitates the connection one of the first to fifth embodiments or a polymer formed by polymerizing the compound contains as at least one structural component.

An eighth embodiment of the present invention provides a compound represented by the following general formula (IA):

In the general formula (IA), Ar ¹ and Ar ^{2 have the} same meaning as described in the general formula (I). -Ar ² -P ⁴ substituted at the 4-position or 5-position of the thiophene ring. P ^{3 represents} a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein one or more of the -CH ₂ - in the alkyl group may be replaced by -O-, -CO-, -NR ¹ -, wherein R ^{1 is} a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, -CH = CH- or -C≡C-, provided that heteroatoms are not adjacent to each other, and the alkyl group may have a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom. P ⁴ denotes -P ^{4 '} -P ⁶ , wherein P ^{6 represents} a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein one or more -CH ₂ - in the alkyl group may be replaced by -O-, -CO- , -CH = CH-, or -C≡C-, with the proviso that heteroatoms are not adjacent to each other, and the alkyl group may have a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom, and P ^{4 '} denotes a divalent electron-attracting group selected from the group consisting of an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfoxy group (-SO ₃ -). D ¹ denotes one selected from the group consisting of an oxygen atom (-O-), a sulfur atom (-S-) and -NP ⁵ -, wherein P ^{5 represents} a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 Carbon atoms, wherein one or more -CH ² - in the alkyl group may be replaced by -O-, -CO-, -CH = CH- or -C≡C-, with the proviso that heteroatoms are not arranged adjacent to each other, and the alkyl group may have a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom, and P ⁵ may be independent of P ³ or may be bonded to P ^{3 to form} a ring. The thiophene ring may have a substituent.

A tenth embodiment of the present invention provides the compound of the ninth embodiment in which Ar ^{1 is} a 1,4-phenylene group and Ar ^{2 is} a 2,6-naphthalene group; or Ar ^{1 is} a 2,6-naphthalene group and Ar ^{2 is} a 1,4-phenylene group.

An eleventh embodiment of the invention provides the compound of the eleventh or twelfth embodiment in which P ³ and P ⁵ each independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

A twelfth embodiment The invention provides an optical element which the compound of the ninth to thirteenth embodiments or a polymer contains the connection.

A thirteenth embodiment of the invention provides a linear optical material that facilitates the connection of a the ninth to thirteenth embodiments or a polymer formed by polymerizing the compound contains as at least one structural component.

A fourteenth embodiment of the invention provides an electro-optic material that facilitates the connection of a the ninth to thirteenth embodiments or a polymer formed by polymerization of the compound contains as at least one structural component.

Examples

The present invention will be described in more detail by way of examples, but should be the scope of the invention should not be so limited.

Synthetic Example 1:

Synthesis of 6- {5- [4- (2-acryloyloxy-ethoxy) -phenyl] -thiophen-2-yl} -naphthalene-2-carboxylic acid 2-acryloyloxy-ethyl ester (Compound 1)

Connection 1

1-Bromo-4-methoxy-benzene (24.1 g, 128.9 mmol) and thiopheneboronic acid (15.0 g, 117.2 mmol) were dissolved in 280 ml of dimethylformamide (DMF) and dissolved in the presence of Pd (PPh ₃ ) ₄ (1.35 g, 1.17 mmol) and potassium carbonate (40.5 g, 293 mmol) at 80 ° C for 10 hours. Then, 300 ml of water was added and extracted with ethyl acetate. After washing with an aqueous saturated solution of sodium chloride, the extracted solution was evaporated over anhydrous magnesium sulfate, and then the solvent was distilled off with a rotary evaporator. Then, the residue was isolated by flash column chromatography using mixed hexane / ethyl acetate = 20/1 solvent to obtain 2- (4-methoxyphenyl) thiophene as white crystals (amount 19.8 g, yield 89.0%).

Then 2- (4-methoxy-phenyl) -thiophene (13.5 g, 70.0 mmol) was dissolved in 120 mL of tetrahydrofuran (THF), to which n-butyllithium (84.8 mmol, 1.6 M hexane solution) was added. gradually added at -78 ° C. After stirring as it was for 1 hour, triethyl borate (B (OEt) ₃ ) was added and stirred at room temperature for 2 hours. Then, an aqueous solution of dilute hydrochloric acid was added and extracted with ethyl acetate. After washing with an aqueous saturated solution of sodium chloride, the extracted solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off by a rotary evaporator to obtain 5- (4-methoxyphenyl) -thiophene-2-boronic acid (14.9 g).

Then, 5- (4-methoxy-phenyl) -thiophene-2-boronic acid (5.42 g, 23.2 mmol) and 6-bromo-naphthalene-2-carboxylic acid methyl ester (6.15 g, 23.2 mmol) in Dissolved 65 ml of dimethylformamide (DMF) and stirred in the presence of Pd (PPh ₃ ) ₄ (266 mg, 0.23 mmol) and potassium carbonate (9.60 g, 69.6 mmol) at 80 ° C for 12 hours. Then, 150 ml of water was added and extracted with ethyl acetate. After purifying with an aqueous saturated solution of sodium chloride, the extracted solution was dried over anhydrous magnesium sulfate and the solvent was distilled off with a rotary evaporator. Then, the residue was isolated by flash column chromatography using mixed hexane / ethyl acetate = 1/1 solvent, to give methyl 6- [5- (4-methoxy-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylate (Amount 5.2 g, yield 61%).

Then methyl 6- [5- (4-methoxy-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylate (4.10 g, 10.9 mmol) was dissolved in 85 mL of dichloromethane, to which 21, 8 ml of 1.0 mol / l dichloromethane solution of boron tribromide (BBr ₃ ) was added dropwise thereto under ice cooling and then stirred at room temperature for 4 hours. Then, water was added to the reaction solution, and the resulting precipitate was filtered and washed with water to obtain 3.80 g of 6- [5- (4-hydroxy-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid.

The Process for the synthesis of the represented by P-S-L in Scheme 2 Connection is shown. Ethylene glycol (18.6 g, 300 mmol) and diisopropylethylamine (58.2 g, 450 mmol) were dissolved in 500 ml of THF and acryloyl chloride (27.2 g, 300 mmol) gradually became to the mixed solution dripped. After stirring Room temperature for For 3 hours, 500 ml of water was added and extracted with ethyl acetate and with aqueous saturated solution washed by sodium chloride. Then the extracted solution became anhydrous Dried magnesium sulfate and the solvent distilled off. The residue was by flash column chromatography using hexane / ethyl acetate = 3/1 mixed solvent isolated and so 2-hydroxyethyl acrylate (Amount 23 g, yield 66%).

2-Hydroxyethyl acrylate (20 g, 172 mmol) and triethylamine (34.8 g, 344 mmol) were dissolved in 250 mL of THF, and methanesulfonyl chloride (23.6 g, 206 mmol) was gradually dropped to the mixed solution. After stirring at room temperature for 5 hours, 250 ml of water was added, extracted with ethyl acetate and washed with an aqueous saturated solution of sodium chloride. Then the extra dried solution over anhydrous magnesium sulfate and the solvent was distilled off to obtain a compound: acrylic acid 2-methanesulfonyloxy-ethyl ester, represented by PSL in Scheme 2.

Finally, 6- [5- (4-hydroxy-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid (200 mg, 0.577 mmol) and 2-methanesulfonyloxy-2-ethyl acrylate (449 mg, 2.31 mmol ) in 5 ml of dimethylformamide in the presence of potassium carbonate (478 mg, 3.46 mmol) heated to 80 ° C and stirred for 8 hours. Then, water was added to the reaction solution, extracted with ethyl acetate, and the extracted solution was washed with an aqueous saturated solution of sodium hydrogencarbonate and an aqueous saturated solution of sodium chloride. The extracted solution (organic layer) was dried over anhydrous magnesium sulfate. It was concentrated with a rotary evaporator and the concentrated solution was purified by silica gel chromatography (developing solution:
Hexane / ethyl acetate = 3/1) to synthesize Compound 1.
FAB-MS: (M + H) ⁺ = 543

If the compound obtained is observed under the polarizing microscope was, it showed liquid crystal properties and showed the following phase transition temperature.

In In the following description, C denotes the crystal, N denotes the nematic phase, S denotes the smectic phase and I denotes the isometric phase.

Synthetic Example 2:

Synthesis of 6- {5- [4- (4-Acryloyloxy-butoxy) -phenyl] -thiophen-2-yl} -naphthalene-2-carboxylic Acid 4-acryloyloxy-butyl Ester (Compound 2)

Connection 2

Acrylic acid 2-methanesulfonyloxy-ethyl ester was replaced by 4-methanesulfonyloxy-butyl acrylate and compound 2 was synthesized in accordance with the method of Synthesis Example 1.
FAB-MS: (M + H) ⁺ = 599

If observed the obtained compound under a polarizing microscope was, it showed liquid crystal properties and showed the following phase transition temperature.

Synthesis Example 3:

Synthesis of 6- {5- {4- (6-acryloyloxy-hexyloxy) -phenyl] -thiophene-2-yl} -q-naphthalene-2-carboxylic acid 6-acryloyloxyhexyl ester (Compound 3)

Acrylic acid 2-methanesulfonyloxy-ethyl ester was replaced by 6-methanesulfonyloxy-hexyl acrylate, and Compound 3 was synthesized in accordance with the procedure of Synthesis Example 1.
FAB-MS: (M + H) ⁺ = 655

If observed the obtained compound under a polarizing microscope was, it showed liquid crystal properties and showed the following phase transition temperature.

Synthetic Example 4:

Synthesis of 6- {5- [4- (12-acryloyloxy-dodecyloxy) -phenyl] -thiophen-2-yl} -naphthalene-2-carboxylic acid 12-acryloyloxy-dodecyl ester (Comp 4)

Connection 4

Acrylic acid 2-methanesulfonyloxy-ethyl ester was replaced by 12-methanesulfonyloxy-dodecyl acrylate, and Compound 4 was synthesized in accordance with the method of Synthesis Example 1.
FAB-MS: (M + H) ⁺ = 823

Synthesis Example 5:

Synthesis of 6- {5- [4- (4-acryloyloxy-butoxy) -phenyl] -thiophen-2-yl} naphthalene-2-carboxylic acid 6-acryloyloxyhexyl ester (Compound 5)

Connection 5

6- [5- (4-Hydroxy-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid (2.0 g, 5.77 mmol) was dissolved in 100 ml of tetrahydrofuran (THF), the Thionyl chloride (820 mg, 6.92 mmol) was added. After stirring at room temperature for 3 hours were 6-hydroxyhexyl acrylate (1.19 g, 6.92 mmol) and triethylamine (1.40 g, 13.8 mmol) were added and at 70 ° C for 4 hours touched. A phosphoric acid buffer was added and extracted with ethyl acetate. After cleaning the extracted solution with an aqueous saturated solution of sodium chloride she was over dried anhydrous magnesium sulfate. After distilling off the solvent it was purified by silica gel chromatography (developing solution: hexane / ethyl acetate = 2/1) to give 6- [5- (4-hydroxy-phenyl-thiophen-2-yl] -naphthalene-2-carboxylic acid 6-acryloyloxy-hexyl ester (1.73 g, 66% yield).

Then, 6- [5- (4-hydroxy-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid 6-acryloyloxy-hexyl ester (1.73 g, 3.46 mmol) and acrylic acid-4-methanesulfonyloxy butyl ester (1.53 g, 6.92 mmol) in dimethylformamide in the presence of potassium carbonate (1.43 g, 10.4 mmol) heated to 80 ° C and stirred for 5 hours. Then, water was added to the reaction solution, extracted with ethyl acetate, and the extracted solution was washed with an aqueous saturated solution of sodium hydrogencarbonate and an aqueous saturated solution of sodium chloride. The extracted solution (organic layer) was dried over anhydrous magnesium sulfate. It was concentrated with a rotary evaporator and the concentrated solution was purified by silica gel chromatography (developing solution: hexane / ethyl acetate = 3/1) to synthesize compound 5.
FAB-MS: (M + H) ⁺ = 627

Synthetic Example 6:

Synthesis of 6- {5- (4- (8-Acryloyloxy-octyloxy) -2-methyl-phenyl] -thiophen-2-yl] -naphthalene-2-carboxylic acid 8-acryloyloxy-octyl ester (Compound 8)

Connection 8

1-Bromo-4-methoxy-benzene was replaced by 4-bromo-1-methoxy-2-methyl-benzene and 2-methanesulfonyloxy-2-ethyl acrylate was replaced by 8-methanesulfonyloxy-octyl acrylate and Compound 8 was made to match synthesized by the method of Synthesis Example 1.
FAB-MS: (M + H) ⁺ = 725
¹ H-NMR (CDCl _3, 300MHz, δ): 1.35 to 1.49 (m, 24H), 1.66 to 1.71 (m, 4H), 1.80 to 1.83 (m, 4H ), 3.97-4.00 (t, J = 6, 6Hz, 2H), 4.14-4.18 (t, J = 6, 6Hz, 4H), 4.37-4.39 (t, J = 6, 6Hz, 2H), 5.80-5.84 (dd, J = 9.6, 1.8Hz, 2H), 6.10-6.20 (dd, J = 13, 2, 1, 8Hz, 2H), 6.37-6.42 (dd, J = 10.2, 1.8Hz, 2H), 6.92-6.95 (d, J = 9, 0Hz, 2H), 7.22 -7.24 (d, J = 3, 9Hz, 1H), 7.44-7.45 (d, J = 2, 7Hz, 1H), 7.56-7.59 (d, J = 8.7Hz , 2H), 7.80-7.88 (dd, J = 8.6, 4.3Hz, 1H), 7.94-7.97 (d, J = 4, 3Hz, 1H), 8.06 ( s, 2H), 8.56 (s, 1H)

If observed the obtained compound under a polarizing microscope was, it showed liquid crystal properties and showed the following phase transition temperature.

Synthesis Example 7:

Synthesis of 4- (5- [6- (6-acryloyloxy-hexyloxy) -naphthalen-2-yl] -thiophen-2-yl} -benzoic acid 6-acryloyloxy-hexyl ester (Compound 13)

Connection 13

1-Bromo-4-methoxy-benzene was replaced by 2-bromo-6-methoxynaphthalene, 6-bromo-naphthalene-2-carboxylic acid methyl ester was replaced by 4-bromo-benzoic acid methyl ester and acrylic acid-2-methanesulfonyloxy ethyl ester was replaced by 6-methanesulfonyloxyhexyl acrylate, and Compound 13 was synthesized in accordance with the procedure of Synthesis Example 1.
FAB - MS: (M + H) ⁺ = 655

Synthetic Example 8:

Synthesis of 4 '- {5- [4- (6-acryloyloxy-hexyloyloxy) -phenyl] -thiophen-2-yl} -biphenyl-4-carboxylic acid 6-acryloyloxyhexyl ester (Compound 15)

Connection 15

Methyl 6-bromo-naphthalene-2-carboxylate was replaced by 4'-bromo-biphenyl-4-carboxylic acid methyl ester and compound 15 was synthesized in accordance with the method of Synthesis Example 3.
FAB - MS: (M + H) ⁺ = 681

Synthetic Example 9:

Synthesis of 6- (5- {4 - [(6-Acryloyloxy-hexyl) -methyl-amino] -phenyl} -thiophen-2-yl) -naphthalene-2-carboxylic acid 6-acryloyloxyhexyl ester (Compound 17)

Connection 17

First 1-bromo-4-methoxybenzene was replaced by N- (4-bromo-phenyl) -N-methyl-acetamide, and 6- {5- {4- (acetylmethyl-amino) -phenyl] -thiophen-2-yl} -naphthalene-2-carboxylic acid methyl ester was in accordance synthesized by the method of Synthesis Example 1.

6- {5- {4- (acetyl-methyl-amino) -phenyl] -thiophene-2-yl} -naphthalene-2-carboxylic acid methylester (4.3 g, 10.3 mmol) was dissolved in 100 ml of dimethylsulfamide containing 10 ml of 5.0 N hydrochloric acid and 20 ml of water were added, dissolved and at 80 ° C for 12 hours touched. Then, water was added to the reaction solution and the precipitate separated by filtration. After washing the precipitate with Ethyl acetate, an aqueous saturated solution of sodium bicarbonate and purified water he was through Dried under vacuum to give 3.38 g of 6- [5- (4-methylaminophenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid.

Finally, 6- [5- (4-methylamino-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid (1.00 g, 2.78 mmol) and 2-methanesulfonyloxyhexyl acrylate (2.78 g) were added g, 11.1 mmol) in 1 ml of dimethylformamide in the presence of potassium carbonate (2.30 g, 16.7 mmol) heated to 80 ° C and stirred for 10 hours. Then, water was added to the reaction solution and extracted with ethyl acetate, and the extracted solution was washed with an aqueous saturated solution of sodium hydrogencarbonate and an aqueous saturated solution of sodium chloride. The extracted solution (organic layer) was dried over anhydrous magnesium sulfate. It was concentrated with a rotary evaporator and the concentrated solution was purified by silica gel chromatography (developing solution:
Hexane / ethyl acetate = 2/1) to synthesize compound 17.
FAB-MS: (M + H) ⁺ = 668

Synthetic Example 10:

Synthesis of 6- (5- {4- (bis (6-acryloyloxy-hexyl) -amino] -phenyl} thiophen-2-yl) -naphthalene-2-carboxylic acid 6-acryloyloxyhexyl ester (Compound 19)

Connection 19

First N- (4-bromo-phenyl) -N-methyl-acetamide was replaced by N- (4-bromo-phenyl-acetamide substituted and 6- [5- (4-acetylaminophenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid methyl ester was in accordance with synthesized by the method of Synthesis Example 9.

Then methyl 6- [5- (4-acetylamino-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylate (1.5 g, 3.74 mmol) in 30 ml of dimethylformamide, containing 5 ml of 5, was added. 0 N hydrochloric acid and 15 ml of water were added, dissolved and stirred at 100 ° C for 24 hours. Then, water was added to the reaction solution and the resulting precipitate was separated by filtration. After washing the precipitate with ethyl acetate, an aqueous saturated solution of sodium hydrogencarbonate and purified water, it was dried by heating under vacuum to give 6- [5- (4-amino-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid receive.

Finally, 6- [5- (4-amino-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid (0.6 g, 1.73 mmol) and 6-methanesulfonyloxyhexyl acrylate (2.6 g, 10.4 mmol) in 10 ml of dimethylformamide in the presence of potassium carbonate (1.43 g, 10.4 mmol) heated to 80 ° C and stirred for 12 hours. Then, water was added to the reaction solution and extracted with ethyl acetate, and the extracted solution was washed with an aqueous saturated solution of sodium hydrogencarbonate and an aqueous saturated solution of sodium chloride. The extracted solution (organic layer) was dried over anhydrous magnesium sulfate. It was concentrated with a rotary evaporator and the concentrated solution was purified by silica gel chromatography (developing solution:
Hexane / ethyl acetate = 3/1) to synthesize compound 19.
FAB-MS: (M + H) ⁺ = 808

Synthesis Example 11:

Synthesis of 6- (5- {4- [4- (acryloyloxy-hexyloxy) -piperidin-1-yl] -phenyl} -thiophen-2-yl) -naphthalene-2-carboxylic acid 6-acryloyloxy-hexyl ester (Compound 20)

Connection 20

4-methoxy-piperidine (12.7 g, 110 mmol) and 1-bromo-4-fluorobenzene (19.3 g, 110 mmol) were dissolved in 150 ml of dimethyl sulfoxide (DMSO) and at 100 ° C for 10 hours in the presence of potassium carbonate (22.8 g, 165 mmol). To Addition of 200 ml of water was extracted with ethyl acetate and washed with an aqueous saturated solution washed by sodium chloride. The extracted solution (organic layer) became anhydrous Dried magnesium sulfate and then the solvent was distilled off. Then the concentrated solution with silica gel chromatography (developing solution: hexane / ethyl acetate = 1/2) purified and so 1- (4-bromo-phenyl) -4-methoxy-piperidine (amount 17.5 g, yield 59%).

Then, 1-bromo-4-methoxybenzene was replaced by 1- (4-bromophenyl) -4-methoxy-piperidine, and Compound 20 was synthesized in accordance with the procedure of Synthesis Example 1.
FAB-MS: (M + H) ⁺ = 738

Synthetic Example 12

Synthesis of compound 23

6 - [- 5- (4-hydroxy-2-methyl-phenyl) -thiophen-2-yl] -naphthalene-3-carboxylic acid synthesized by the method described in Synthetic Example 6.

Then the resulting 6- [5- (4-hydroxy-2-methyl-phenyl) -thiophen-2-yl] -naphthalene-2-carboxylic acid (1.4 g, 3.9 mmol) and the methanesulfonic acid decyl ester (2, 76 g, 11.7 mmol) in 20 ml of dimethylformamide in the presence of potassium carbonate (2.1 g, 15 mmol) heated to 70 ° C and stirred for 10 hours. Then, water was added to the reaction solution and extracted with ethyl acetate, and the extracted solution was washed with an aqueous saturated solution of sodium hydrogencarbonate and an aqueous saturated solution of sodium chloride. The extracted solution (organic layer) was dried over anhydrous magnesium sulfate. It was concentrated with a rotary evaporator, and the concentrated solution was purified by silica gel chromatography (developing solution:
Hexane / ethyl acetate = 5/1) to obtain compound 23 (1.8 g, yield 62%).
FAB-MS: (M + H) ⁺ = 641

When the resulting compound 23 was observed under a polarizing microscope, it exhibited liquid crystal properties and exhibited the following phase transition temperature. Further, S _C denotes the smectic phase C and SA denotes the smectic phase A.

Synthetic Example 13

Synthesis of Compound 24

First were 4-bromo-2-methyl-phenylamine (25g, 134mmol) and 1-bromooctane (26 g, 134 mmol) in DMSO in the presence of potassium carbonate (37 g, 268 mmol). Then, 150 ml of water was added and extracted with ethyl acetate. After washing with an aqueous saturated solution of sodium chloride, the extracted solution was dried over anhydrous magnesium sulfate dried and the solvent distilled off with a rotary evaporator. Then the residue became with flash column chromatography using hexane / ethyl acetate = 5/1 mixed solvent purified to give (4-bromo-2-methyl-phenyl) -octylamine (28.7 g, Yield 72%).

Then was (4-bromo-2-methyl-phenyl) -methyl-octyl-amine (28.7 g, 96.2 mmol) stirred with iodomethane (27 g, 192 mmol) and so (4-bromo-2-methyl-phenyl) -methyl-octyl-amine (25 g, yield 85%). The purification was performed by flash column chromatography (developing solution: hexane / ethyl acetate = 10/1).

Then, 1-bromo-4-methoxybenzene was replaced by (4-bromo-2-methyl-phenyl) -methyl-octyl-amine (25 g, 81 mmol) and 5- [3-methyl-4- (methyl- octyl-amino) -phenyl] -thiophene-2-boronic acid was synthesized in accordance with the method of Synthesis Example 1. The resulting 5- [3-methyl-4-methyl-octyl-amino) -phenyl] -thiophene-2-boronic acid (5.4 g, 15 mmol) and the octyl 6-bromo-naphthalene-2-carboxylate (5 , 8 g, 16 mmol) were dissolved in 30 ml of DMF and stirred in the presence of Pd (PPh ₃ ) ₄ (184 mg, 0.16 mmol) and potassium carbonate (4.4 g, 32 mmol) and kept at 80 for 12 h ° C stirred. Then, 50 ml of water was added and extracted with ethyl acetate. After purifying with an aqueous saturated solution of sodium chloride, the extracted solution was dried over anhydrous magnesium sulfate and the solvent was distilled off with a rotary evaporator. Then, it was isolated by flash column chromatography using hexane / ethyl acetate = 1/1 mixed solvent to obtain the objective compound 24.
FAB-MS (M + H) ⁺ = 598

Other compounds of the invention can also in agreement be synthesized by the method of Synthesis Example 1.

example 1

One Builder material containing 6- {5- [4- (4-acryloyloxybutoxy) -phenyl] -thiophen-2-yl} -naphthalene-2-carboxylic acid 4-acryloyloxy-butyl ester (Compound 2) (92.7 parts by weight), phenothiazine (1.3 parts by weight), a polymerization initiator (Illugacure 651, trade name of products manufactured by Ciba Geigy (4 parts by weight) and hydroquinone monomethyl ether (2 parts by weight) contained in a horizontally oriented cell at a distance of 4 μm, a glass substrate with transparent ITO electrode parts, formed by applying a thin Polyimide film as an insulating film included (manufactured by E.H.I). Then, the obtained sample was kept at 160 ° C, while between the transparent electrodes a DC voltage of 200 V was applied, and W irradiation (254 nm, 10 W / cm, 3 min) was performed.

infrared light a YAG laser (1.6 μm) was irradiated to the sample obtained as described above, to confirm the generation of second harmonic waves. The intensity The second harmonic wave of the sample was made for one Maintained month.

Example 2

A chloroform solution containing 6- {5- [4- (4-acryloyloxy-butoxy) -phenyl] -thiophen-2-yl} -naphthalene-2-carboxylic acid 4-acryloyloxy-butyl ester (Compound 2) (92.7 wt Parts), phenothiazine (1.3 parts by weight), a polymerization initiator (Illugacure 651, trade name of products manufactured by Ciba Geigy Co.) (4 parts by weight) and hydroquinone monomethyl ether (2 parts by weight ) was spin-coated (1000 rpm, 20 sec) on a glass substrate having ITO transparent electrode portions formed by applying a polyimide film as an insulating film, and then dried under reduced pressure for 12 hours. Then, the obtained sample was kept at 160 ° C and the tension was measured using ei A corona poling process (applied voltage: 5.0 kV, 20 min) was applied, and then W irradiation (254 nm, 10 W / cm, 3 min) was performed while the voltage was applied. An aluminum electrode was vapor-deposited on a crosslinked non-linear optical response part to make a non-linear optical material having electrodes at both ends.

infrared light a YAG laser (1.06 μm) was irradiated to the sample obtained as described above, to the generation of second harmonic waves and the electro-optical Effects to confirm. The intensity the second harmonic waves and the electro-optical effect the sample was for maintained for a month.

3 shows the intensity of the second harmonic waves before and after the corona sweep for the sample obtained as described above.

Out From the examples described above, it can be seen that the crosslinkable Connection useful is remarkable as an organic non-linear optical material with suppressed Aging waste for the electro-optical effect or the generation of second harmonic Waves.

Example 3

The compound 23 was placed in a horizontally oriented cell having a 5 μm gap and comprising a glass substrate having an ITO transparent electrode portion (manufactured by EH I). Then, the obtained sample was kept at 70 ° C while applying a DC voltage of 150 V between the transparent electrodes. Infrared light of a YAG laser (1.06 μm) was irradiated on the obtained sample to confirm generation of second harmonic waves. 4 Figure 4 shows the intensity of the second harmonic waves for the sample obtained as described above and for the sample 5CB for use as a reference oriented under electric fields under the same conditions.

in the With regard to the sample, it can be seen that the nonlinear invention optical connection better non-linear optical properties as the rod-like liquid crystal compound 5CB (reference compound) in a state of orientation in one owns electric field and it is useful as an organic, non-linear optical material.

The The present invention can provide (1) a novel compound which can be used is considered a non-linear optical material that is organic Material with no or controlled orientation translation includes, (2) a novel compound useful as a nonlinear one optical material used in orientation in an electrical Field generates second harmonic waves and (3) an optical element, a non-linear optical material and an electro-optical material using the crosslinked product or non-crosslinked product the connection available put.

Claims (12)

Compound represented by the following general formula (I):

wherein: -Ar ² -AS ² -P ² substitutes the 4-position or 5-position of a thiophene ring; Ar ¹ and Ar ² each independently represents a single bond, an aromatic ring having 5 to 14 carbon atoms or a biphenyl group, provided that at least one of Ar ¹ and Ar ^{2 represents} one of a naphthalene ring and a biphenyl group having a substituent can; D is an oxygen atom (-O-), a sulfur atom (-S-), a substituted amino group (-NR-), in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or one by P ¹ -S ¹ represented substituents or an amino group having a cyclic structure; and A represents an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfonyloxy group (-SO ₃ -); Each of S ¹ and S ² independently represents a divalent linking group; Each of P ¹ and P ² is independently a substituent consisting of atoms selected from C, H, O, N, S and a halogen atom; at least one of P ¹ and P ^{2 represents} a polymerizable group including an acryloyloxy group or a methacryloyloxy group; and the thiophene ring may have a substituent. A compound according to claim 1, wherein: Ar ^{1 represents} a benzene ring and Ar ^{2 represents} a naphthalene ring; or Ar ^{1 represents} a naphthalene ring and Ar ^{2 represents} a benzene ring. A compound according to claim 1 or 2, wherein each of S ¹ and S ² independently represents an alkylene group having 2 to 12 carbon atoms. Optical element comprising the compound according to a the claims 1 to 3 or a polymer of this compound. Nonlinear optical material comprising as at least a component of the compound according to one of claims 1 to 3 or a polymer formed by polymerizing the compound becomes. Electro-optical material comprising as at least a component of the compound according to one of claims 1 to 3 or a polymer formed by polymerizing the compound becomes. Compound represented by the following general formula (IA):

wherein: Ar ¹ and Ar ² each independently represent a single bond, an aromatic ring having 5 to 14 carbon atoms or a biphenyl group, provided that at least one of Ar ¹ and Ar ^{2 represents} a naphthalene ring and a biphenyl group having a substituent can; -Ar ² -P ⁴ substituted the 4-position or 5-position of a thiophene ring; P ^{3 represents} a linear, branched or cyclic alkyl group having from 1 to 20 carbon atoms, wherein one or more of the -CH ₂ - in the alkyl group may be replaced by -O-, -CO-, -NR ¹ -, wherein R ^{1 is} a linear is a branched or cyclic alkyl group having 1 to 20 carbon atoms, -CH = CH- or -C≡C-, provided that heteroatoms are not adjacent to each other, and the alkyl group may have a substituent selected from the atoms selected from C, H, O, N, S and a halogen atom; P ⁴ -P ^{4 '} -P ⁶ , wherein: P ^{6 represents} a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein one or more of the -CH ₂ - in the alkyl group by -O-, -CO-, -CH = CH- or -C≡C- may be substituted, provided that heteroatoms are not adjacent to each other, and the alkyl group may have a substituent selected from the atoms selected from C, H, O, N, S and a Halogen atom exists; and P ^{4 'represents} a divalent electron attracting group selected from the group consisting of an ester group (-COO-), a sulfonyl group (-SO ₂ -) and a sulfoxy group (-SO ₃ -); D ^{1 is} one selected from the group consisting of an oxygen atom (-O-), a sulfur atom (-S-) and -NP ⁵ - in which P ^{5 is} a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms wherein one or more of the -CH ₂ - in the alkyl group may be replaced by -O-, -CO-, -CH = CH- or -C≡C-, provided that heteroatoms are not adjacent to each other, and Alkyl group may have a substituent consisting of the atoms selected from C, H, O, N, S and a halogen atom, and P ⁵ may be independent of P ³ or may be bonded to P ^{3 to form} a ring; and the thiophene ring may have a substituent. A compound according to claim 7, wherein: Ar ^{1 is} a 1,4-phenylene group and Ar ^{2 is} a 2,6-naphthalene group; or Ar ^{1 is} a 2,6-naphthalene group and Ar ^{2 is} a 1,4-phenylene group. A compound according to claim 7 or 8, wherein P ³ and P ⁵ each independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Optical element comprising the compound according to a the claims 7 to 9 or a polymer of this compound. Nonlinear optical material comprising as at least a component of the compound according to one of claims 7 to 9 or a polymer formed by polymerizing the compound becomes. Electro-optical material comprising as at least a component of the compound according to one of claims 7 to 9 or a polymer formed by polymerizing the compound becomes.